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61.
Complexes of Vanadium and Titanium with Salicylaldehyde benzoylhydrazone and 2-(2′-Hydroxyphenyl)-8-quinolinol. Crystal Structure of μ-Oxo-bis[oxo{2-(2′-hydroxyphenyl)-8-quinolinato(2-)}-vanadium(V)] . By reaction of titanium(IV)-isopropoxide and bis(acetylacetonato)-oxovanadium(IV) with salicylaldehyde benzoylhydrazone and 2-(2′hydroxyphenyl)-8-quinolinol, respectively, the metal complexes of the tridentate diacidic ligands were synthesized and characterized mass spectrometrically. The mass spectra of the titanium compounds correspond to the expected bisligand complexes whereas several species are demonstrable in the case of vanadium. Crystals of μ-oxo-bis[oxo{2-(2′-hydroxyphenyl)-8-quinolinolato(2-)}-vanadium(V)] were isolated and characterized by X-ray structural analysis. The complex exhibits C2 symmetry, accordingly the μ2-oxygen atom is situated on the 4 axis. The VOV bridge is angular with the unusually small bond angle of 107.3°. The coordination polyhedron is distorted octahedral. The compound additionally contains one molecule of chloroform per formula unit which is disordered in two positions. Crystallographic data see “Inhaltsübersicht”. 相似文献
62.
Silvia Schaffner Ludwig Macko Markus Neubufger Margareta Zehnder 《Helvetica chimica acta》1997,80(2):463-471
Crystal and solution structures of the enantiomerically pure and the racemic pairs of (η3-allyl) {2-[2′-(diphenylphosphino)phenyl]-4,5-dihydro-4-phenyloxazole}palladium(II) hexafluorophosphates ( 1 , and rac- 1 , resp.) and tetraphenylborates ( 2 , and rac- 2 , resp.) as well as (η3-allyl){2-[2′-(diphenylphosphino)phenyl]-4,5-dihydro-4-isopropyloxazole}palladium(II) tetraphenylborate ( 3 ) were characterized by X-ray crystallography and 1H-NMR spectroscopy. In the solid state, rac- 1 and rac- 2 proved to be disordered with both diastereoisomeric complexes in the crystal. The complexes 2 and 3 exist only in the ‘exo’ form. The X-ray structures show that the [PdII(η3-allyl)] moiety may adopt different configurations between a nearly symmetrical three-electron PdII(π3-allyl) system and an asymmetrical allyl group with a η1- and a η2-bonding to the metal center. The [PdII(η3-allyl)] system of rac- 1 and of ‘endo’ rac- 2 is closer to the former, and that of 2 , ‘exo’-rac- 2 , and 3 closer to the later geometry. The 1H-NMR spectra of the hexafluorophosphates 1 and rac- 1 show two sets of signals of the allylic protons in an ‘exo’/‘endo’ ratio of 2:3. The tetraphenylborates 2, rac- 2 , and 3 give only one set of broad signals of the allylic protons. 相似文献
63.
Yang Nan Subhash P. Upadhyaya Wei Xu Kathrine E. Hughes William J. Dunn Ludwig Bauer Hemendra N. Bhargava George A. Doss 《Journal of heterocyclic chemistry》1996,33(2):399-407
A number of (E)-7-arylidenenaltrexones were synthesized by azeotropic distillation of water from a benzene solution of naltrexone and an aromatic aldehyde (benzaldehyde, 4-chloro- and 4-fluorobenzaldehyde, 3-and 4-pyridinecarboxaldehyde and 1-methyl-2-imidazolecarboxaldehyde) using piperidine as a catalyst. In addition, (E)-7-benzylidenenaloxone was prepared by the previously published Claisen-Schmidt condensation using sodium hydroxide in methanol. The stereochemistry of these arylidene derivatives 3–9 was determined to be (E) by means of nuclear Overhauser enhancement experiments. The 13C nmr spectra of (E)- 3–9 are recorded in deuteriochloroform and those of the hydrochlorides in deuteriodimethyl sulfoxide. 相似文献
64.
It is shown by proton NMR and quantum chemical PCILO calculations that monothio-β-ketones in solution exist as different isomers depending on substituents, solvent and temperature. In solvents with low dielectric constants the hydrogen-bridged cis enol form predominates, and is in fast equilibrium (in the NMR scale) with nonchelated trans enol forms down to ?100°C at least. Transition enthalpies are of the order of 7–15 kJ mol?1. In compounds with R2 = Me the rotation of the Me -CS group around the neighbouring C-C- bond can be detected and the thermodynamic and kinetic parameters estimated. The reason for the slowing down of this rotation, inferred from the line broadening in NMR, is probably the stabilization of a trans isomer by interaction between the protons of the methyl group and the lone pairs of the oxygen atom. There are no indications for the presence of chelated and non-chelated enethiol isomers from the PMR studies and quantum chemical calculations performed. 相似文献
65.
We used a combination of theoretical and experimental methods to derive the spectroscopic properties of imidazolium-based ionic liquids. Vibrational frequencies, NMR chemical shifts, and quadrupole coupling constants react in comparable manner to changes in the chemical environment. This suggests that both the IR and the NMR spectroscopic properties reflect a similar type of electronic perturbation caused by hydrogen bonding. These relationships of the spectroscopic properties provide detailed information about structural complexes and may thus serve as good indicators of ion-pair formation. They also help to decide which spectroscopic tool is the most sensitive for investigating molecular interactions. The measurement of only one spectroscopic property allows the prediction of other properties that cannot be so easily measured. In some cases, this is the only way to obtain reliable coupling constants for deriving molecular correlation times from macroscopic NMR relaxation times, thus opening a new path for studying structure-dynamics relations in ionic liquids. 相似文献
66.
Ludwig Maier 《Helvetica chimica acta》1968,51(7):1608-1616
Further examples of the α-aminoalkylation of white phosphorus and of a biphosphine are reported. The reaction is described using C-methyl piperidines, methylamine, ethylamine or propylamine as the amine component, and formaldehyde or benzaldehyde as the carbonyl component. The reaction mechanism has been clarified. Furthermore the direct synthesis of the diethylamine salt of phosphorous acid is reported. In addition, some physical and chemical properties of tris (dialkylamino-methyl)-phosphine oxides are given and their coordination compounds with nickel halides are described. 相似文献
67.
New Oxonium Bromochalcogenates(IV) — Synthesis, Structure, and Properties of [H3O][TeBr5] · 3 C4H8O2 and [H3O]2[SeBr6] Dark red crystals of the composition [H3O][TeBr5] · 3 C4H8O2 ( 1 ) were isolated from a saturated solution of TeBr4 in 1,4-dioxane containing a small amount of water. In this compound (space group P21/m, a = 8.922(4) Å, b = 13.204(7) Å, c = 9.853(5) Å, β = 91.82(4)° at 150 K) a square pyramidal [TeBr5]? anion has been isolated for the first time. The coordination sphere of the anion is completed to a distorted octahedron by weak interaction with a dioxane molecule of the cationic system. The [H3O]+ cations are connected to chains by dioxane molecules. At room temperature the compound is stable only in its mother liquor. Crystalline [H3O]2[SeBr6] ( 2 ) (space group Fm3m, a = 10.421(1) Å at 170 K) is a bromoselenous acid of high symmetry. The [H3O]+ ion is only weakly coordinated by Br atoms of the anion. The anions are isolated octahedral [SeBr6]2? units. The structure is isotypic to the K2[PtCl6] structure. Despite being a halogenochalcogen(IV) acid, 2 exhibits a remarkable thermal stability. Both oxonium compounds were characterized by single-crystal X-ray structure analyses. Vibrational spectra of 2 are reported. 相似文献
68.
2-Vinylindole ( 1a ) and its donor- and acceptor-substituted (E)-derivatives 1b – e react highly locoselectively with dimethyl 1,2,4,5-tetrazine-3,6-dicarboxylate ( 3 ) to form the novel (indol-2-yl)-1,4-dihydropyridazines 4a and 7 as well as the heterocyclic annellated pyridazines 4b , 5 , and 6 . The reactions of the structurally related 3-vinylindoles 2a – e with 3 also gave rise to new indol-3-ylpyridazines 8 , 9 , and 10 . The locoselectivities of these Diels-Alder reactions were controlled mainly by steric effects. 相似文献
69.
Determination of traces of iridium with thiodibenzoylmethane by substoichiometric isotope dilution analysisIridium(III or IV) reacts with thiodibenzoylmethane on heating at pH 6 to form a 1:3 complex, which can be concentrated by extraction into chloroform. Based on this reaction, a reproducible, selective determination of iridium is achieved by means of substoichiometric isotope dilution analysis, based on 192Ir. The linear range is 1–11 nmol of iridium. 相似文献
70.